KR20120089686A - Substrate for printed wiring and resin composition used therefor - Google Patents

Abstract

The present invention provides a printed wiring board, a printed wiring laminate, and a resin composition used to manufacture the substrate, the laminate, which are excellent in light transmittance, heat resistance, mechanical strength, and heat coloring property. The solution of the present invention is a printed wiring board comprising an aromatic polyether polymer having a glass transition temperature of 230 ° C to 350 ° C as measured by differential scanning calorimetry (DSC, heating rate 20 ° C / min).

Description

Substrate for printed wiring and resin composition used for it {SUBSTRATE FOR PRINTED WIRING AND RESIN COMPOSITION USED THEREFOR}

The present invention relates to a printed wiring board and a resin composition used therefor.

Flexible as an electronic wiring material to be used in recent years, according to the miniaturization and weight reduction of mobile phones, digital cameras, navigators, and other electronic devices, and fine pitch of wiring patterns formed on a substrate. In addition to high functionalization of printed wiring boards (FPC boards), specifically heat resistance and flexibility, glass-level light transmittance and adhesion to wiring sections are required.

As a polymer for forming a flexible printed wiring board, the wholly aromatic polyimide (The Kaneka Co., Ltd. Apical etc.) as conventionally shown by (patent document 1), for example has been used.

However, since the substrate containing polyimide is colored yellowish brown by the formation of charge transfer complexes in and between molecules, it has been difficult to apply to applications requiring glass-level light transmission.

Moreover, when shape | molding a polyimide to a film, it is necessary to imidize at the temperature of 300-500 degreeC.

Japanese Patent Laid-Open No. 2002-322298

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a printed wiring board excellent in light transmittance, heat resistance, mechanical strength, and heat coloring property, a printed wiring laminate using the substrate, and a resin composition used to manufacture the substrate. It aims to do it.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that the said subject of this invention could be solved by the board for printed wirings using the polymer which has a specific structural unit, and completed this invention.

That is, this invention provides the following [1]-[12].

[1] A printed wiring board comprising an aromatic polyether polymer having a glass transition temperature of 230 ° C to 350 ° C as measured by differential scanning calorimetry (DSC, heating rate 20 ° C / min).

[2] The aromatic polyether polymer is a polymer having at least one structural unit (iii) selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2): The board | substrate for printed wirings of 1].

<Formula (1)>

(In formula (1), R <^1> -R <^4> represents a C1-C12 monovalent organic group each independently, R <^9> represents a C1-C12 monovalent organic group each independently, R <^10> is a cyano group or Nitro group, a to d each represent an integer of 0 to 4, i represents an integer of 0 to 3)

<Formula (2)>

(Formula (2):, R ¹ to R ⁴ and a to d each independently is R ¹ to R ⁴ and a to d and agreement in the formula (1), Y represents a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, g and h each independently represent an integer of 0 to 4, and m is 0 Or 1)

[3] [1] or the polymer further having at least one structural unit (ii) selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4): The board for printed wirings described in [2].

<Formula 3>

(In formula (3), R <^9> , R <^10> and i are respectively independently synonymous with R <^9> , R <^10> and i in the said General formula (1), and R <^5> and R <^6> are respectively independently C1-C12 1 Represents an organic group, Z represents a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e and f represents an integer of 0 to 4, respectively, n represents 0 or 1)

<Formula 4>

(In formula (4), R <^7> , R <^8> , Y, m, g, and h are respectively independently synonymous with R <^7> , R <^8> , Y, m, g, and h in said Formula (2), R <^5> , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in formula (3))

[4] The printed wiring board according to [3], wherein the molar ratio of the structural unit (i) and the structural unit (ii) in the polymer is 30:70 to 90:10.

[5] The printed wiring board according to [3] or [4], wherein the polymer contains 70 mol% or more of the structural unit (i) and the structural unit (ii).

[6] The printed wiring board according to any one of [1] to [5], wherein the total light transmittance in the JIS K7105 transparency test method is 50% or more in a thickness of 50 µm.

[7] The printed wiring board according to any one of [1] to [6], wherein the tensile strength in JIS K7127 is 80 to 150 MPa.

[8] The printed wiring board according to any one of [1] to [7], wherein the elongation at break in JIS K7127 is 10 to 100%.

[9] The printed wiring board according to any one of [1] to [8], wherein the tensile modulus in JIS K7127 is 2.5 to 4.0 GPa.

[10] A printed wiring laminate provided with a wiring portion on the printed wiring board according to any one of [1] to [9].

[11] A substrate for printed wiring board containing a polymer having at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2), and an organic solvent: Resin composition.

<Formula (1)>

(In formula (1), R <^1> -R <^4> represents a C1-C12 monovalent organic group each independently, R <^9> represents a C1-C12 monovalent organic group each independently, R <^10> is a cyano group or Nitro group, a to d each represent an integer of 0 to 4, i represents an integer of 0 to 3)

<Formula (2)>

(Formula (2):, R ¹ to R ⁴ and a to d each independently is R ¹ to R ⁴ and a to d and agreement in the formula (1), Y represents a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, g and h each represent an integer of 0 to 4, and m is 0 or 1 Indicates

[12] The printed wiring according to [11], wherein the polymer further has at least one structural unit selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4): Resin composition for substrate formation.

<Formula 3>

(In formula (3), R <^9> , R <^10> and i are respectively independently synonymous with R <^9> , R <^10> and i in the said General formula (1), and R <^5> and R <^6> are respectively independently C1-C12 1 Represents an organic group, Z represents a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e and f represents an integer of 0 to 4, respectively, n represents 0 or 1)

<Formula 4>

(In formula (4), R <^7> , R <^8> , Y, m, g, and h are respectively independently synonymous with R <^7> , R <^8> , Y, m, g, and h in said Formula (2), R <^5> , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in formula (3))

Since the board | substrate for printed wirings of this invention contains the heat resistant polymer excellent in transparency and moldability, it is high in light transmittance and excellent in heat resistance and heat-coloring resistance. Therefore, it can be used suitably for conductor flexible printed wiring boards, such as a mobile telephone, a touch panel, electronic paper, a rigid printed wiring board, an optoelectronic printed wiring board, a chip on film (COF) board, a board for tape automated bonding (TAB), etc. have.

The printed wiring board of the present invention comprises an aromatic polyether polymer having a glass transition temperature (glass transition point) measured by differential scanning calorimetry (DSC, heating rate 20 ° C / min) of 230 ° C to 350 ° C. The glass transition temperature of the said polymer is specifically measured by the 8230 type DSC measuring apparatus (heating rate 20 degree-C / min) by Rigaku Corporation, Preferably it is 240-330 degreeC, More preferably, it is 250-300 degreeC.

Moreover, the said aromatic polyether type polymer is a polymer obtained by reaction which forms an ether bond in a principal chain.

Since the board | substrate which consists of such an aromatic polyether type polymer has the outstanding heat resistance and heat-coloring resistance, it is used suitably for printed wiring, especially the board for printed wiring which can be applied to the process which becomes 220 degreeC or more temperature, such as a solder reflow process. It is preferably used as. Moreover, since the said aromatic polyether polymer is excellent in moldability, the board | substrate which consists of the said polymer is used suitably as a board | substrate for printed wirings. In addition, in this invention, "thermal coloring resistance" means that coloring is difficult when heat-processing for 1 to 3 hours at high temperature (220-300 degreeC) in air | atmosphere.

The aromatic polyether polymer is a polymer having at least one structural unit (i) selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2) (hereinafter referred to as "polymer ( Also referred to as "I)". Since a polymer has a structural unit, it becomes aromatic polyether whose glass transition temperature is 230-350 degreeC. Since this polymer (I) is excellent in transparency and heat-coloring resistance, the board | substrate which consists of the said polymer is high in light transmittance, and is excellent in heat-coloring resistance. Moreover, the board | substrate which consists of a polymer (I) is a board | substrate which is excellent in adhesiveness with conductive layers, such as a wiring part provided in the surface, and is hard to produce distortion and a fall of mechanical strength even at high temperature, and it is dimensional stability under high humidity. This is excellent. Therefore, it is used suitably for printed wiring.

<Formula (1)>

In the formula (1), R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, R ⁹ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and R ¹⁰ represents a cyano group or nitro Group, a to d each represent an integer of 0 to 4, and i represents an integer of 0 to 3;

Examples of the monovalent organic group having 1 to 12 carbon atoms include a monovalent hydrocarbon group having 1 to 12 carbon atoms and a monovalent hydrocarbon group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. Can be mentioned.

As a C1-C12 monovalent hydrocarbon group, a C1-C12 linear or branched hydrocarbon group, a C3-C12 alicyclic hydrocarbon group, a C6-C12 aromatic hydrocarbon group, etc. are mentioned.

As said C1-C12 linear or branched hydrocarbon group, a C1-C8 linear or branched hydrocarbon group is preferable, and a C1-C5 linear or branched hydrocarbon group is more preferable.

Specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group is mentioned.

As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable and a C3-C4 alicyclic hydrocarbon group is more preferable.

As a specific example of a C3-C12 alicyclic hydrocarbon group, Cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; Cycloalkenyl groups, such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group, are mentioned. The linking site of the alicyclic hydrocarbon group may be any alicyclic carbon.

As said C6-C12 aromatic hydrocarbon group, a phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

As a C1-C12 hydrocarbon group containing an oxygen atom, a C1-C12 hydrocarbon group etc. which have an ether bond, a carbonyl group, and an ester group are mentioned.

As a C1-C12 hydrocarbon group which has an ether bond, a C1-C12 alkoxy group, a C2-C12 alkenyloxy group, a C2-C12 alkynyloxy group, a C6-C12 aryloxy group, and carbon number 1-12 alkoxyalkyl group etc. are mentioned. Specifically, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, a methoxymethyl group, etc. are mentioned.

Moreover, as a C1-C12 hydrocarbon group which has a carbonyl group, a C2-C12 acyl group etc. are mentioned. Specifically, an acetyl group, a propionyl group, an isopropionyl group, a benzoyl group, etc. are mentioned.

As a C1-C12 hydrocarbon group which has an ester group, a C2-C12 acyloxy group etc. are mentioned. Specifically, an acetyloxy group, a propionyloxy group, an isopropionyloxy group, a benzoyloxy group, etc. are mentioned.

As a C1-C12 hydrocarbon group containing a nitrogen atom, an imidazole group, a triazole group, a benzimidazole group, a benztriazole group, etc. are mentioned.

As a C1-C12 hydrocarbon group containing an oxygen atom and a nitrogen atom, an oxazole group, an oxadiazole group, a benzoxazole group, a benzoxadiazole group, etc. are mentioned specifically ,.

<Formula (2)>

Formula (2) of R ¹ to R ⁴ and a to d is R ¹ to R ⁴ and a to d and the consent of each independently represent the formula (1), Y represents a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, g and h each represent an integer of 0 to 4, and m represents 0 or 1 Indicates. When m is 0, it is preferable that R <^7> is not a cyano group and a nitro group.

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same functional groups as described above.

Further, the polymer (I) may further have at least one structural unit (ii) selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4). When the said polymer (I) has such a structural unit (ii), the board | substrate for printed wirings containing the said polymer (I) is preferable because a mechanical characteristic improves.

<Formula 3>

Formula (3) of the R ^9, R ¹⁰ and i are each independently selected from the formula (1) of the R ^9, R ¹⁰ and R i and consent, R ⁵ and R ⁶ is a monovalent group having 1 to 12 carbon atoms, each independently An organic group, Z represents a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e and f Represents an integer of 0 to 4, respectively, and n represents 0 or 1.

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same functional groups as described above.

The divalent organic group having 1 to 12 carbon atoms includes at least one atom selected from the group consisting of a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom and a nitrogen atom. And a C3-C12 divalent halogenated hydrocarbon group containing at least one atom selected from the group consisting of a C3-C12 divalent hydrocarbon group and an oxygen atom and a nitrogen atom.

As a C1-C12 bivalent hydrocarbon group, a C1-C12 linear or branched bivalent hydrocarbon group, a C3-C12 bivalent alicyclic hydrocarbon group, a C6-C12 divalent aromatic hydrocarbon group, etc. Can be mentioned.

Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include methylene group, ethylene group, trimethylene group, isopropylidene group, pentamethylene group, hexamethylene group and heptamethylene group.

As a C3-C12 divalent alicyclic hydrocarbon group, Cycloalkylene groups, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group; Cycloalkenylene groups, such as a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group, etc. are mentioned.

As a C6-C12 bivalent aromatic hydrocarbon group, a phenylene group, a naphthylene group, a biphenylene group, etc. are mentioned.

As a C1-C12 bivalent halogenated hydrocarbon group, a C1-C12 linear or branched bivalent halogenated hydrocarbon group, a C3-C12 divalent halogenated alicyclic hydrocarbon group, and a C6-C12 divalent halogenation Aromatic hydrocarbon group etc. are mentioned.

Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include difluoromethylene group, dichloromethylene group, tetrafluoroethylene group, tetrachloroethylene group, hexafluorotrimethylene group, hexachlorotrimethylene group and hexa Fluoroisopropylidene group, hexachloroisopropylidene group, etc. are mentioned.

As a C3-C12 divalent halogenated alicyclic hydrocarbon group, the group by which at least one hydrogen atom of the group illustrated in the said C3-C12 divalent alicyclic hydrocarbon group was substituted by the fluorine atom, the chlorine atom, the bromine atom, or the iodine atom. Etc. can be mentioned.

Examples of the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms include a group in which at least a part of the hydrogen atoms of the groups exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Can be mentioned.

As a C1-C12 bivalent hydrocarbon group containing at least 1 sort (s) of atom chosen from an oxygen atom and a nitrogen atom, C1-C12 bivalent hydrocarbon group which has an ether bond, a carbonyl group, ester group, and an amide group is mentioned.

As a C1-C12 divalent halogenated hydrocarbon group containing at least 1 sort (s) of atom chosen from the group which consists of an oxygen atom and a nitrogen atom, a C1-C12 divalent hydrocarbon containing an oxygen atom and / or a nitrogen atom specifically, The group by which at least one hydrogen atom of the group illustrated in the group was substituted by the fluorine atom, the chlorine atom, the bromine atom, or the iodine atom is mentioned.

<Formula 4>

In the formula ^{(4) R 7, R 8} , Y, m, g , and h is ^{R 7, R 8, Y,} m, g , and h with consent of each independently represents the formula (2), R ^5, R ⁶ , Z, n, e and f are each independently synonymous with R <^5> , R <^6> , Z, n, e and f in the said General formula (3). When m is 0, it is preferable that R <^7> is not a cyano group and a nitro group.

In the polymer (I), the molar ratio of the structural unit (i) and the structural unit (ii) (wherein the sum of them is 100) is (i) :( ii) = 30: 70 from the viewpoint of heat resistance and mechanical properties. It is preferable that it is -90: 10, It is more preferable that it is (v) :( ii) = 40: 60-90: 10, It is still more preferable that it is (v) :( ii) = 50: 50-90: 10. .

In the present invention, the mechanical properties refer to properties such as tensile strength, breaking elongation and tensile modulus of the polymer.

It is preferable that the said polymer (I) contains 70 mol% or more of the said structural unit (iii) and the said structural unit (ii), and it is more preferable that 95 mol% or more of all the structural units are included.

The polymer (I) is, for example, a compound represented by the following general formula (A) (hereinafter also referred to as "compound (A)") and a compound represented by the following general formula (8) (hereinafter also referred to as "compound (8)") A component containing at least one compound selected from the group consisting of (hereinafter referred to as "(A) component") and a compound represented by the following formula (B) (hereinafter also referred to as "component (B)") Can be obtained by reacting

<Formula (A)>

In said Formula (A), R <^9> , R <^10> and i are respectively independently synonymous with R <^9> , R <^10> and i in the said Formula (1), and X represents a halogen atom independently.

<Formula 8>

Formula (8) and of ^{R 7, R 8, Y,} m, g , and h is ^{R 7, R 8, Y,} m, g , and h with consent of each independently represents the formula (2), X has the formula It is synonymous with X in (A).

<Formula (B)>

R ^b in the formula (B) each independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group, or a trifluoromethylsulfonyl group, and among these, a hydrogen atom is preferable.

In addition, the R ¹ to R ⁴ and a to d are R ¹ to R ⁴ and a to d and the consent of each independently represent the formula (1) in the formula (B).

Specific examples of the compound (A) include 2,6-difluorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,5 -Dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-difluoronitrobenzene, 2,5-difluoronitrobenzene, 2,4-difluoronitrobenzene, 2,6-dichloronitrobenzene , 2,5-dichloronitrobenzene, 2,4-dichloronitrobenzene, and reactive derivatives thereof are mentioned. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoint of reactivity and economy. These compounds can also be used in combination of 2 or more type.

Specifically as said compound (8), 4,4'- difluoro benzophenone, 4,4'- difluoro diphenyl sulfone, 2,4'- difluoro benzophenone, 2,4'- difluoro di Phenylsulfone, 2,2'-difluorobenzophenone, 2,2'-difluorodiphenylsulfone, 3,3'-dinitro-4,4'-difluorobenzophenone, 3,3'-di Nitro-4,4'-difluorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenylsulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenylsulfone , 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenylsulfone, 3,3'-dinitro-4,4'-dichlorobenzophenone and 3,3'-dinitro-4,4'- Dichlorodiphenyl sulfone etc. are mentioned. These compounds can also be used in combination of 2 or more type.

The at least one compound selected from the group consisting of the compound (A) and the compound (8) preferably contains 80 mol% to 100 mol% in 100 mol% of the component (A), and contains 90 mol% to 100 mol%. It is more preferable.

In addition, the component (B) preferably contains a compound represented by the following general formula (9) (hereinafter also referred to as "compound (9)"), and preferably contains a compound represented by the following general formula (10). desirable. It is preferable that 80 mol%-100 mol% are contained in 100 mol% of (B) component, and, as for compound (9), it is more preferable that 90 mol%-100 mol% are contained.

<Formula (9)>

In the formula (9), R ¹ to R ⁴ and a to d is R ¹ to R ⁴ and a to d and the consent of each independently represent the formula (1).

Specific examples of the compound (9) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene and 9,9-bis (3 , 5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl ) Fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, reactive derivatives thereof, and the like. Among the above compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can also be used in combination of 2 or more type.

<Formula 10>

^{R 5, R 6, Z,} n, e , and f of the general formula 10 is ^{R 5, R 6, Z,} n, e , and f with consent of each independently represent the formula (3).

Examples of the compound represented by the formula (10) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4'-biphenol, 3,3'-biphenol, 4,4'-dihydroxydiphenylsulfone, 3 , 3'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, 1,1'-bi-2-naphthol, 1,1'-ratio 4-naphthol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane, reactive derivatives thereof, and the like. These compounds can also be used in combination of 2 or more type.

Among the above-mentioned compounds, 4,4'-biphenol is preferably used from the viewpoint of reactivity and mechanical properties.

The said polymer (I) can be synthesize | combined more specifically by the method shown below.

Compound (9) contained in component (B) is reacted with an alkali metal compound in an organic solvent to obtain an alkali metal salt of compound (9), followed by the obtained alkali metal salt and compound (A) contained in component (A) and / or Compound (8) is reacted. In addition, the reaction between the compound (9) and the alkali metal compound is carried out in the presence of the compound (A) and / or the compound (8) to thereby cause the alkali metal salt of the compound (9) and the compound (A) and / or the compound (8). It can also react.

As an alkali metal compound used for reaction, Alkali metals, such as lithium, potassium, and sodium; Alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride; Alkali metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide; Alkali metal carbonates, such as lithium hydrogen carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate, etc. are mentioned. These can also be used combining 1 type (s) or 2 or more types.

The alkali metal compound has an amount of metal atoms in the alkali metal compound, usually 1 to 3 equivalents, preferably 1.1 to 2 equivalents, more preferably 1.2 to 1.5 times, relative to one -OR ^b in the formula (B). Used in equivalent amounts.

As the organic solvent used for the reaction, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyllactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (alkoxy group has 1 to 4 carbon atoms) ) And trialkoxybenzene (the alkoxy group has 1 to 4 carbon atoms) or the like. Among these solvents, polar organic solvents having high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenyl sulfone and dimethyl sulfoxide are particularly preferably used.

In the reaction, a solvent which is azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phentol may be further used. .

The proportion of the component (A) and the component (B) is preferably from 45 mol% to 55 mol%, more preferably from 45 mol% to less than 55 mol%, when the total amount of the components (A) , More preferably 50 mol% or more and 52 mol% or less, still more preferably 50 mol% or more and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, Or more and 50 mol% or less, and more preferably 48 mol% or more and less than 50 mol%.

Moreover, reaction temperature becomes like this. Preferably it is 60 degreeC-250 degreeC, More preferably, it is the range of 80 degreeC-200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

The aromatic polyether polymer is low in the process load of the polymer because the high temperature treatment for imidization, which is necessary for the synthesis of the polyimide polymer, is unnecessary, and thus the polymer can be easily produced.

Preferably, the aromatic polyether polymer has a polystyrene equivalent weight average molecular weight (Mw) measured by a TOSOH HLC-8220 GPC device (solvent: N-methyl-2-pyrrolidone added with lithium bromide and phosphoric acid). 5,000 to 500,000, more preferably 15,000 to 250,000.

The resin composition of this invention contains the said polymer (I) and an organic solvent, It is characterized by the above-mentioned.

The mixture of polymer (I) and the organic solvent obtained by the said method can be used as it is as the resin composition of this invention for manufacturing the said board for printed wirings. By using such a resin composition, the board | substrate for printed wiring can be manufactured easily and inexpensively.

The resin composition of the present invention may also be prepared by isolating (purifying) the polymer as a solid component from a mixture of the polymer (I) and the organic solvent obtained by the above method, and then re-dissolving it in an organic solvent. By using such a resin composition, the board | substrate for printed wirings with less coloring and excellent in light transmittance can be manufactured.

The method for isolating (purifying) the polymer (I) as a solid component is, for example, by reprecipitation of the polymer in a poor solvent of a polymer such as methanol, followed by filtration and subsequent drying of the filtrate under reduced pressure. I can do it. As the organic solvent for dissolving the polymer (I), for example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and γ-butyrolactone is preferably used, and methylene chloride, N, N-dimethylacetamide and N-methylpyrrolidone are more preferably used from the viewpoint of coatability and economical efficiency. These solvents can be used alone or in combination of two or more.

Although the polymer concentration in the resin composition of this invention which melt | dissolved the said polymer (I) changes with molecular weight of a polymer, it is 5 to 40 weight% normally, Preferably it is 7 to 25 weight%. If it is less than 5 weight%, it is hard to thicken and there exists a possibility that a pinhole may be easily produced. On the other hand, when it exceeds 40 weight%, the viscosity of a resin composition is too high, it is difficult to form into a film, and surface smoothness may be inadequate.

In addition, although the viscosity of the resin composition of this invention changes also with the molecular weight and concentration of a polymer, it is normally 2,000-100,000 mPa * s, Preferably it is 3,000-50,000 mPa * s. If it is less than 2,000 mPa * s, the retention property of the resin composition in film-forming is bad and may flow from a support body. On the other hand, when it exceeds 100,000 mPa * s, viscosity may become high too much and adjustment of a film thickness becomes difficult, and shaping | molding of the board | substrate for printed wiring may become difficult.

Moreover, the resin composition of this invention can further contain an antioxidant, and can improve the durability of the board for printed wirings obtained by containing an antioxidant.

As an anti-aging agent, Hindered phenol type compound of molecular weight 500 or more is mentioned preferably.

Examples of the hindered phenolic compound having a molecular weight of 500 or more that can be used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6- Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy- 3,5-di-tert-butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1, 1,3-tris [2-methyl-4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane, 2,2- Thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnaamide), 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4 -Hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10- [tetraoxaspiro [5.5] undecane etc. are mentioned. These anti-aging agents can be used individually by 1 type or in combination of 2 or more types.

In this invention, it is preferable to use the hindered phenol type compound of molecular weight 500 or more with respect to 100 weight part of said polymers (I) in the quantity of 0.01-10 weight part.

The board | substrate for printed wirings of this invention contains the polymer of the said aromatic polyether type polymer. Although the board | substrate for printed wirings of this invention may contain an additive other than the polymer of this invention according to a desired use, it is preferable that it consists essentially of only the polymer of this invention.

Although the manufacturing method of the printed wiring board of this invention is not restrict | limited, It includes the process of apply | coating the said resin composition on a support body, and forming a coating film, and the process of removing and removing a film by evaporating the said organic solvent from the said coating film, and obtaining a film. desirable.

As a method of apply | coating the said resin composition on a support body, and forming a coating film, the roll coating method, the gravure coating method, the spin coating method, the method using a doctor blade, etc. are mentioned.

Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers. As said support body, a polyethylene terephthalate (PET) film, a SUS board, etc. are mentioned.

In addition, the process of removing the said organic solvent by evaporating the said organic solvent can be performed by heating a coating film specifically. By heating the coating film, the organic solvent in the coating film can be removed by evaporation. What is necessary is just to evaporate the organic solvent, and just to determine suitably according to a support body or a polymer, The heating conditions are preferable, for example, it is preferable that heating temperature is 30 degreeC-300 degreeC, It is more preferable that it is 40 degreeC-250 degreeC, It is more preferable that it is -230 degreeC.

Moreover, as heating time, it is preferable that they are 10 minutes-5 hours. In addition, heating can also be performed in two or more steps. Specifically, it is dried for 10 minutes to 2 hours at a temperature of 30 to 80 ° C, and then further heated for 10 minutes to 2 hours at 100 ° C to 250 ° C. Moreover, you may dry in nitrogen atmosphere or pressure_reduction | reduced_pressure as needed.

The amount of residual solvent in the substrate obtained after the step of removing the organic solvent (thermogravimetric analysis: TGA, temperature rise rate 10 ° C / min under nitrogen atmosphere) is preferably 0 to 1.2% by weight relative to 100% by weight of the substrate. Preferably it is 0-1 weight%. When the amount of residual solvent is in this range, the board | substrate which is excellent in heat resistance and hard to produce deformation | transformation and mechanical strength fall even in especially high temperature can be obtained. Therefore, the said board | substrate is used suitably for a printed wiring.

The obtained film can be peeled off from the support and used as a printed wiring board, or can be used as a printed wiring board without being peeled off.

As for the printed wiring board of this invention, it is preferable that the glass transition temperature (Tg) by Rigaku Corporation 8230 type DSC measuring apparatus (heating rate 20 degree-C / min) is 230-350 degreeC, and it is more preferable that it is 240-330 degreeC. It is more preferable that it is 250-300 degreeC. If glass transition temperature exists in such a range, it can use more preferably for printed wiring.

Preferably the thickness of the board for printed wirings in this invention is 1-250 micrometers, More preferably, it is 2-150 micrometers, More preferably, it is 10-125 micrometers.

When the board | substrate for printed wirings of this invention is 50 micrometers in thickness, it is preferable that the total light transmittance in JISK7105 transparency test method is 85% or more, and it is more preferable that it is 88% or more. The total light transmittance can be measured using a SC-3H type haze meter manufactured by Sugashi Kenki Co., Ltd ..

When the thickness of a printed wiring board of this invention is 50 micrometers, the light transmittance in wavelength 400nm becomes like this. Preferably it is 70% or more, More preferably, it is 75% or more, More preferably, it is 80% or more. The light transmittance at a wavelength of 400 nm can be measured using a V-570 type UV / VIS / NIR spectrometer manufactured by JASCO.

It is preferable that tensile strength of the printed wiring board of this invention is 80-150 MPa, It is more preferable that it is 85-130 MPa, It is further more preferable that it is 85-120 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

It is preferable that break elongation of the printed wiring board of this invention is 5 to 100%, It is more preferable that it is 10 to 100%, It is further more preferable that it is 15 to 100%. Break elongation can be measured using the tensile tester 5543 (made by INSTRON company).

It is preferable that it is 2.5-4.0 GPa, and, as for the board | substrate for printed wirings of this invention, it is more preferable that it is 2.7-3.7 GPa. Tensile modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

It is preferable that phase difference of the printed wiring board of this invention is 50 nm or less, It is preferable that it is 0.1-10 nm, It is more preferable that it is 0.2-5 nm. The phase difference can be measured using a RETS spectrometer (manufactured by Otsuka Denshi Co., Ltd.).

It is preferable that it is 15 ppm / K or less, and, as for the board | substrate for printed wirings of this invention, it is more preferable that it is 5-12 ppm / K. Humidity expansion coefficient can be measured using MA (TII-SS6100, humidity control option manufactured by SII Nanotechnology). If the humidity expansion coefficient of a board | substrate exists in the said range, since it shows that the dimensional stability of a board | substrate under high humidity is high, it can use more preferably for printed wiring.

The printed wiring laminated body of this invention is obtained by providing a wiring part on the said board for printed wiring. Such a printed wiring laminate of the present invention is excellent in adhesion between the substrate and the wiring portion when the printed wiring board and the wiring portion including the polymer (I) are included.

As a method of forming a wiring part, a copper layer, indium tin oxide (ITO), polythiophene, polyaniline, polypyrrole, etc. are formed on a film by the lamination method, the metallizing method, sputtering method, the vapor deposition method, the coating method, the printing method, etc., for example. The method of providing the wiring part which consists of an electroconductive material of this is mentioned.

In the lamination method, the printed wiring board provided with the conductive layer can be manufactured by, for example, hot pressing a metal foil such as copper foil to the printed wiring board of the present invention, and the printed wiring provided with the wiring portion by etching the conductive layer. A wiring board can be manufactured.

In the metallizing method, for example, a seed layer containing a Ni-based metal bonded to the printed wiring board of the present invention is formed by a vapor deposition method or a sputtering method, and copper having a predetermined film thickness is formed on the seed layer by a wet plating method or the like. By providing conductive layers, such as a printed wiring board, the printed wiring board with which the conductive layer was provided can be manufactured, and the printed wiring board with a wiring part can be manufactured by etching this conductive layer. In addition, when using the metallizing method, in order to improve the adhesiveness of metals, such as Ni, it is preferable to previously surface-modify the board | substrate for printed wirings of this invention by plasma processing etc.

In the sputtering method, for example, a printed wiring for which a conductive layer is provided by applying a DC high voltage or the like between a printed wiring board and a target such as indium tin oxide (ITO) while introducing an inert gas into a vacuum, for example. A board | substrate can be manufactured and the board | substrate for printed wiring in which a wiring part was provided can be manufactured by etching this electrically conductive layer.

In the vapor deposition method, for example, a printed wiring board with a wiring portion can be manufactured by vaporizing a precursor of a substance to be formed into a film and depositing it on a printed wiring board.

In addition, in the coating method and the printing method, for example, a solution containing a target conductive material is applied to a printed wiring board using a roll coating method, a gravure coating method, a spin coating method, a doctor blade, a screen printing machine, an inkjet printer By the method of printing by a dispenser, a flexographic printing machine, a gravure printing machine, etc., the board | substrate for printed wiring in which the wiring part was provided can be manufactured.

When the printed wiring laminate of the present invention peels off the wiring part in the MIT anti-rupture test (ASTM D2176, temperature 23 ° C., humidity 50%, bending angle ± 135 °, bending speed 100 times / min, load 250g, bending radius 3mm) The number of bends up to is preferably 15,000 or more, more preferably 30,000 or more (also, the number of bends is bent to a position of +135 degrees from the initial 0 degree position (a state where the substrate for printed wiring is horizontal). Again bends to -135 degrees via 0 degrees and then returns to 0 degrees in one operation).

In the printed wiring laminate of the present invention, the number of times of the cold test until the wiring portion is peeled off in the cold test is preferably more than 15 times, more preferably 10 or more times. In a constant temperature room set to a predetermined temperature (240 ° C.), held for 30 minutes, taken out, and returned to room temperature for one hour.

Since the board | substrate for printed wirings of this invention contains the heat resistant polymer excellent in transparency and moldability, it is high in light transmittance and excellent in heat resistance and heat-coloring resistance. Therefore, it can be used suitably for conductor flexible printed wiring boards, such as a mobile telephone, a touch panel, an electronic paper, a rigid printed wiring board, an optoelectronic printed wiring board, a COF (chip on film) board, a TAB (Tape Automated Bonding) board, etc. Can be.

The printed wiring board (printed wiring laminate) is usually mounted thereon with mounting components such as functional components, large-scale integrated circuits (LSI), and / or circuit components, and is embedded in electronic devices. In this case, positioning is performed in advance on the printed wiring board, and mounting components are mounted on the positioned portion.

In a conventional printed wiring board having a wiring pattern having a wide wiring pitch width, it is not required that the precision of the mounting position at the time of this mounting is very high. However, due to the high functionality, miniaturization, and light weight of electronic devices, when mounting the mounting component on a printed wiring board having a fine pitch with a narrow wiring pitch width, high precision is required for the mounting position.

At present, in order to mount a mounting component on a board | substrate with high precision, the method of grasping the position of a mounting component and mounting it on a board | substrate using transmitted light, etc. is used, The printed wiring laminated which has a wiring pattern whose pitch width is 30 micrometers or less It is desired to have a high total light transmittance as a body substrate.

When the printed wiring board of the present invention has a thickness of 50 μm, the total light transmittance in the JIS K7105 transparency test method is in the above range, and heat resistance, thermal coloring resistance, mechanical strength, insulation, dimensional stability, adhesion to the wiring part, and the like are Since it is excellent, it is especially used suitably as a board | substrate for printed wirings which has a wiring pattern whose pitch width is 30 micrometers or less.

<Examples>

Hereinafter, the present invention will be described in detail with reference to examples.

(1) structural analysis

The structural analysis of the polymer obtained in the following example was performed by IR (ATR method, FT-IR, 6700, NICOLET company make).

(2) weight average molecular weight

The weight average molecular weight of the polymer obtained by the following example and the comparative example was measured using the TOSOH HLC-8220 type GPC apparatus. N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used as a solvent, and polystyrene conversion molecular weight was calculated | required at the measurement temperature of 40 degreeC.

(3) optical properties

(3a) total light transmittance

The total light transmittance of the film obtained by the following example and the comparative example was measured according to JISK7105 transparency test method. Specifically, it measured using the SC-3H type haze meter by the Sugashi Kenki Corporation.

(3b) light transmission

The transmittance | permeability in wavelength 400nm of the film obtained by the following example and the comparative example was measured using the V-570 type UV / VIS / NIR spectrometer by JASCO Corporation.

(3c) optical anisotropy

The phase difference of the film obtained by the following example and the comparative example was measured using the OTSKADENSHI company RETS spectrometer. Evaluation of phase difference The film thickness was shown by the value normalized to 100 micrometers.

(4) Heat resistance

(4a) glass transition point

The glass transition points of the polymers and films obtained in the following Examples and Comparative Examples were measured using a 8230 type DSC measuring apparatus manufactured by Rigaku, with a temperature increase rate of 20 ° C / min.

(4b) heat colorability

The heat coloring property of the film obtained by the following example and the comparative example was judged by the presence or absence of the coloring of the film after heat-processing at 230 degreeC in air | atmosphere for 2 hours.

(5) mechanical characteristics

Tensile strength, breaking elongation, and tensile modulus of the films obtained in the following Examples and Comparative Examples were measured using a tensile tester 5543 (manufactured by INSTRON) in accordance with JIS K7127.

(6) forming processability

Preparation of the film from the polymer obtained by the following example and the comparative example was performed with the following method. The resin composition was applied onto a support made of polyethylene terephthalate (PET) using a doctor blade so as to have a film thickness of 50 ± 10 μm, dried at 80 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes. After peeling off from a PET support, it was made into a film. Thereafter, the film was fixed to a metal frame, and the final drying was performed by drying at 150 to 300 ° C. for 2 hours depending on the type of polymer. Evaluation of molding processability was performed by the film external appearance and the amount of residual solvent ((thermal gravimetric analysis method: TGA), temperature rising rate 10 degree-C / min in nitrogen atmosphere).

In addition, as a result of observing visual observation as a result of visual observation, when "(circle)" was observed by "(circle)" and visual observation as a result of visual observation, the case where a flaw, curvature, and curvature were observed was made into "x".

(7) Adhesion with conductive layer

The film (5 cm x 10 cm) obtained by the following example and the comparative example was fixed to the metal frame, and it installed in the sputtering apparatus. The film surface was then plasma treated. Plasma treatment was carried out in argon gas at a frequency of 13.56 MHz, an output of 200 W, a gas pressure of 1 × 10 ⁻³ Torr, a temperature of 2 ° C. at the time of treatment, and a treatment time of 2 minutes. Subsequently, using a target of a nickel-chromium (chromium 10% by mass) alloy under a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 3 x 10 ^-3 Torr, at a speed of 1 nm / second by DC magnetron sputtering under an argon atmosphere A nickel-chromium alloy film (seed layer) having a thickness of about 10 nm was formed, and copper was subsequently deposited to form a copper thin film having a thickness of 0.3 μm. Further, a copper layer having a thickness of 10 μm was further formed on the surface of the copper thin film using a copper sulfate plating bath, and then heat-treated and dried at 150 ° C. for 10 minutes to produce a printed wiring board having a conductive layer formed on one surface thereof.

And the adhesiveness of the film of the obtained printed wiring board and a conductive layer was evaluated on the following references | standards.

(Seasonal test)

The bending test was done about the board | substrate for printed wirings with which the conductive layer was formed in the obtained one surface in the environment of the temperature of 23 degreeC, and 50% of humidity. Test conditions were carried out in accordance with the MIT internal testing (ASTM D2176).

The bending radius was 3 mm at a bending angle of ± 135 °, a bending speed of 100 times / min, and a load of 250 g. In addition, the number of bends is bent from the initial 0 degree position (the state where the substrate for printed wiring is horizontal) to the +135 degree position, and again bent to the -135 degree position via the 0 degree position, and then the 0 degree position. The operation to return to was performed once.

The number of times until the film and the conductive layer of the printed wiring board having the conductive layer formed on one side were peeled off was measured. When the number of bends exceeded 30,000 times, no breakage or cracking occurred. "(Circle)" and the case where fracture | rupture and a crack generate | occur | produce within 30,000 times as the frequency | count of a bending | flexion generate | occur | produced within 15,000 or more and 30,000 times were made into "x."

(Cold test)

The cold heat test was done about the board | substrate for printed wirings with which the conductive layer was formed in one obtained surface. In the cold test, the substrate was placed in a constant temperature chamber set at a predetermined temperature (240 ° C.), held for 30 minutes, then taken out, and returned to room temperature for one hour. The number of times until the film and the conductive layer of the formed printed wiring board were peeled off was measured.

"◎" indicates that no peeling, rupture or cracking occurs even if the number of cold test times exceeds 15, and "○" indicates that peeling, rupture or cracking occurs within 15 or more times of the cold test times. The case where fracture | rupture and a crack generate | occur | produce in less than 10 times of tests was made into "x".

(8) environmental stability (humidity expansion coefficient)

The humidity expansion coefficients of the films obtained in the following Examples and Comparative Examples were measured under the following conditions using the MA (SII Nanotechnology, TMA-SS6100) humidity control option.

Humidity condition: 40% RH → 70% RH (tension method: load 5 g) Temperature: 23 degrees Celsius

Example 1 Preparation of Aromatic Polyether Resin

(B) Component: 9, 9-bis (4-hydroxyphenyl) fluorene (70.08 g, 200 mmol), in a 1000 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube. (A) Component: 2, 6- difluoro benzonitrile (27.82 g, 200 mmol), potassium carbonate (33.17 g, 240 mmol), 550 mL of N-methyl- 2-pyrrolidone (NMP), and 270 mL of toluene were added. Subsequently, after nitrogen-substituting the flask, the resulting solution was reacted at 130 ° C, and the resulting water was removed by a Dean-Stark tube. The temperature was raised gradually to 160 degreeC when water generation was not observed, and it was made to react for 5 hours as it is.

After cooling to room temperature, the mixture was placed in a large amount of methanol, and the filtrate (residue) was isolated by filtration fractionation. The resulting filtrate was vacuum dried at 60 ° C. overnight to give a white powder (polymer) (83.61 g, 93% yield).

About the obtained polymer, structural analysis, the glass transition point, and the weight average molecular weight were measured. The results showed that the characteristic absorption in the infrared spectrum was 2229, 1575, 1500 cm ^-1 , the glass transition point was 285 ° C., and the weight average molecular weight was 107,000.

Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc), and the resin composition of 15 mass% was obtained. The resin composition was applied onto a support made of polyethylene terephthalate (PET) using a doctor blade, dried at 80 ° C. for 30 minutes, then dried at 150 ° C. for 60 minutes to form a film, and then peeled from the PET support. . Then, the film was fixed to a metal frame, and it dried further at 200 degreeC for 2 hours, and obtained the film for evaluation with a film thickness of 50 micrometers.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

In addition, Table 1 and Table 2 show the results of the optical properties, heat resistance, mechanical properties, molding processability, adhesiveness, and environmental stability of the obtained film.

(Example 2)

9,9-bis (4-hydroxyphenyl) fluorene (63.07 g, 180 mmol) and 4,4'-biphenol instead of 9,9-bis (4-hydroxyphenyl) fluorene (70.08 g, 200 mmol) A white powder (polymer) was obtained in the same manner as in Example 1 except that (3.72 g, 20 mmol) was used (79.69 g, yield 92%), and the film thickness was measured in the same manner as in Example 1 using the polymer. A 50 μm film for evaluation was obtained.

Characteristic absorption of the infrared spectrum of the obtained polymer was 2229, 1573, 1455 cm <^-1> , glass transition point was 270 degreeC, and the weight average molecular weight was 127,000.

Moreover, the obtained polymer had the outstanding solubility with respect to the organic solvent (DMAc).

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

(Example 3)

9,9-bis (4-hydroxyphenyl) fluorene (42.05 g, 120 mmol) and 4,4'-biphenol instead of 9,9-bis (4-hydroxyphenyl) fluorene (70.08 g, 200 mmol) A white powder (polymer) was obtained in the same manner as in Example 1 except for using (14.90 g, 80 mmol) (72.16 g, yield 94%), and the film thickness was measured in the same manner as in Example 1 using the polymer. A 50 μm film for evaluation was obtained.

Characteristic absorption of the infrared spectrum of the obtained polymer was 2229, 1573, 1455 cm <^-1> , glass transition point was 245 degreeC, and the weight average molecular weight was 131,000.

Moreover, the obtained polymer had the outstanding solubility with respect to the organic solvent (DMAc).

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

(Example 4)

In a 3 L four-necked flask, (A) component: 2,6-difluorobenzonitrile (hereinafter also referred to as "DFBN") 35.12 g (0.253 mol), (B) component: 9,9-bis (4-hydride) Oxyphenyl) fluorene (hereinafter also referred to as "BPFL") 70.08 g (0.200 mol), resorcinol (hereinafter also referred to as "RES") 5.51 g (0.050 mol), potassium carbonate 41.46 g (0.300 mol), N 443 g of, N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Subsequently, a four-necked flask was attached with a thermometer, a stirrer, a three-way coke with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube.

Subsequently, after nitrogen-substituting the flask, the resulting solution was reacted at 140 ° C for 3 hours, and the resulting water was removed from the Dean-Stark tube at any time. The temperature was raised gradually to 160 degreeC when water generation was not observed, and it was made to react for 6 hours as it is.

After cooling to room temperature (25 ° C.), the resulting salt was removed with a filter paper, the filtrate was put in methanol to reprecipitate, and the filtrate (residue) was isolated by filtration fractionation. The filtrate obtained was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (amount 95.67 g, yield 95%).

The structural analysis and the weight average molecular weight of the obtained polymer were performed. The results indicate that the characteristic absorption in the infrared absorption spectrum is 3035 (CH stretch), 2229 cm ^-1 (CN), 1574 cm ^-1 , 1499 cm ^-1 (aromatic ring skeleton absorption), 1240 cm ^-1 (-O-), and the weight average molecular weight is 130,000.

Then, the obtained polymer was redissolved in DMAc and the resin composition of 25 mass% of polymer concentrations was obtained. The resin composition was applied onto a support made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, then dried at 100 ° C. for 30 minutes to form a film, and then peeled from the PET support. . Thereafter, the film was fixed to a metal frame and further dried at 230 ° C. for 2 hours to obtain a film for evaluation having a film thickness of 50 μm.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 5)

It carried out similarly to Example 4 except having used 11.41 g (0.050 mol) of 2, 2-bis (4-hydroxyphenyl) propane instead of resorcinol, and the film for evaluation was obtained. In addition, the weight average molecular weight of the obtained polymer was 98,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 6)

9,9-bis (4-hydroxyphenyl) fluorene 78.84 g (0.225 mol) and 2,2-bis (4-hydroxyphenyl) -1, instead of 70.08 g of BPFL and 5.51 g of RES as component (B), The film for evaluation was obtained like Example 4 except having used 8.41 g (0.025 mol) of 1,1,3,3,3-hexafluoropropane. In addition, the weight average molecular weight of the obtained polymer was 105,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 7)

(B) Evaluation was carried out in the same manner as in Example 4, except that 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene was used instead of 70.08 g of BPFL and 5.51 g of RES as components (B). A film was obtained. In addition, the weight average molecular weight of the obtained polymer was 146,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 8)

(B) 78.84 g (0.225 mol) of 9,9-bis (4-hydroxyphenyl) fluorene and 6.71 bis (4-hydroxyphenyl) cyclohexane instead of 70.08 g of BPFL and 5.51 g of RES as components (B) Except having used g (0.025mol), it carried out similarly to Example 4 and obtained the film for evaluation. In addition, the weight average molecular weight of the obtained polymer was 78,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 9)

As in Example 7, except that 28.10 g (0.202 mol) of 2,6-difluorobenzonitrile and 11.02 g (0.051 mol) of 4,4-difluorobenzophenone were used as the component (A) instead of 35.12 g of DFBN. It carried out and obtained the film for evaluation. In addition, the weight average molecular weight of the obtained polymer was 122,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 10)

Evaluation was performed in the same manner as in Example 9 except that the compounding amount of component (A) was changed to 17.56 g (0.126 mol) of 2,6-difluorobenzonitrile and 27.55 g (0.126 mol) of 4,4-difluorobenzophenone. A film for use was obtained. In addition, the weight average molecular weight of the obtained polymer was 157,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Example 11)

It carried out similarly to Example 7 except having used 78.84 g (0.250 mol) of 4, 4- difluoro diphenyl sulfone (DFDS) as (A) component, and the film for evaluation was obtained. In addition, the weight average molecular weight of the obtained polymer was 132,000.

Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2.

The obtained polymer had excellent solubility in an organic solvent (DMAc).

(Comparative Example 1)

2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoro instead of 9,9-bis (4-hydroxyphenyl) fluorene (70.08 g, 200 mmol) A white powder (polymer) was obtained in the same manner as in Example 1 except that propane (67.25 g, 200 mmol) was used (81.85 g, yield 94%), and the same membrane as in Example 1 was used using the polymer. The film for evaluation of thickness 50micrometer was obtained.

The glass transition point of the obtained polymer was 190 degreeC, and the weight average molecular weight was 159,000. Evaluation of the obtained film was performed by the method similar to Example 1. The results are shown in Table 1 and Table 2. In addition, the cold-heat test could not be measured because the board | substrate for printed wiring in which the conductive layer was formed in the obtained one surface was deformed.

(Comparative Example 2)

Theonex (polyethylene naphthalate film manufactured by Teijin Co., Ltd.) was used as the film for evaluation, and evaluation was performed by the method similar to Example 1 (film thickness 125 micrometers). The results are shown in Table 1 and Table 2. In addition, the cold-heat test could not be measured because the board | substrate for printed wiring in which the conductive layer was formed in the obtained one surface was deformed.

(Comparative Example 3)

9.70 g (23.6 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to a 300 mL four-necked flask equipped with a thermometer, agitator, nitrogen inlet tube and cooling tube. Subsequently, after nitrogen-substituting the flask, NMP (60 ml) was added and stirred until it became uniform. 5.30 g (23.6 mmol) of 2,3,5-tricarboxycyclopentyl acetic anhydride dianhydride was added to the obtained solution at room temperature, stirring was continued for 12 hours at that temperature, and the solution containing polyamic acid was obtained.

NMP (75 ml) was added and diluted to the solution containing the obtained polyamic acid, pyridine (7.5 ml) and acetic anhydride (6.7 ml) were added, and it stirred at 110 degreeC for 6 hours, and imidated. Then, after cooling to room temperature, it put into a large amount of methanol and isolate | separated the filtrate by filtration fractionation. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (amount 13.5 g, yield 95.3%).

Then, the obtained polymer was redissolved in DMAc and the resin solution of 20 mass% was obtained. The resin solution was applied onto a support made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, then dried at 150 ° C. for 60 minutes to form a film, and then PET. Peeled from the support. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain a film for evaluation having a film thickness of 50 μm. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 and Table 2.

It can be seen from Table 2 that the film including the aromatic polyether polymer having a glass transition temperature of 230 ° C to 350 ° C is excellent in molding processability. In addition, the film comprising an aromatic polyether polymer having a glass transition temperature of 230 ° C. to 350 ° C. has a high light transmittance and balances dimensional change (environmental stability), heat resistance, mechanical strength, and adhesion to the conductive layer due to absorption. And excellent ones are shown (Examples 1 to 11). On the other hand, it can be seen that the film of Comparative Example 1 does not have sufficient heat resistance and adhesion to the conductive layer, and the film of Comparative Example 2 does not have sufficient heat resistance, poor light transmittance, and large anisotropy. Moreover, the film of the comparative example 3 was inferior to heat-coloring resistance, adhesiveness with a conductive layer, and water absorption resistance.

Claims (12)

The printed wiring board which contains the aromatic polyether polymer whose glass transition temperature measured by differential scanning calorimetry (DSC, temperature rising rate 20 degree-C / min) is 230 degreeC-350 degreeC. The aromatic polyether polymer according to claim 1, wherein the aromatic polyether polymer has at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2): A printed wiring board which is a polymer.
<Formula (1)>

(In formula (1), R <^1> -R <^4> represents a C1-C12 monovalent organic group each independently, R <^9> represents a C1-C12 monovalent organic group each independently, R <^10> is a cyano group or Nitro group, a to d each represent an integer of 0 to 4, i represents an integer of 0 to 3)
<Formula (2)>

(Formula (2):, R ¹ to R ⁴ and a to d each independently is R ¹ to R ⁴ and a to d and agreement in the formula (1), Y represents a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, g and h each represent an integer of 0 to 4, and m is 0 or 1 Indicates The method according to claim 1 or 2, wherein the polymer further comprises at least one structural unit (ii) selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4). The printed wiring board which has.
<Formula 3>

(In formula (3), R <^9> , R <^10> and i are respectively independently synonymous with R <^9> , R <^10> and i in the said General formula (1), and R <^5> and R <^6> are respectively independently C1-C12 1 Represents an organic group, Z represents a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e and f represents an integer of 0 to 4, respectively, n represents 0 or 1)
<Formula 4>

(In formula (4), R <^7> , R <^8> , Y, m, g, and h are respectively independently synonymous with R <^7> , R <^8> , Y, m, g, and h in said Formula (2), R <^5> , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in formula (3)) The printed wiring board of Claim 3 whose molar ratio of the said structural unit (i) and the said structural unit (ii) is 30: 70-90: 10 in the said polymer. The printed wiring board according to claim 3 or 4, wherein the polymer contains 70 mol% or more of the structural unit (i) and the structural unit (ii). The printed wiring board according to any one of claims 1 to 5, wherein the total light transmittance in the JIS K7105 transparency test method is 50% or more in a thickness of 50 µm. The printed wiring board according to any one of claims 1 to 6, wherein the tensile strength in JIS K7127 is 80 to 150 MPa. The board | substrate for printed wirings in any one of Claims 1-7 whose break elongation in JISK7127 is 10 to 100%. The printed wiring board according to any one of claims 1 to 8, wherein the tensile modulus in JIS K7127 is 2.5 to 4.0 GPa. The printed wiring laminated body in which the wiring part was provided on the board | substrate for printed wirings of any one of Claims 1-9. A resin composition for forming a substrate for printed wiring, comprising a polymer having at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2), and an organic solvent: .
<Formula (1)>

(In formula (1), R <^1> -R <^4> represents a C1-C12 monovalent organic group each independently, R <^9> represents a C1-C12 monovalent organic group each independently, R <^10> is a cyano group or Nitro group, a to d each represent an integer of 0 to 4, i represents an integer of 0 to 3)
<Formula (2)>

(Formula (2):, R ¹ to R ⁴ and a to d each independently is R ¹ to R ⁴ and a to d and agreement in the formula (1), Y represents a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group, g and h each represent an integer of 0 to 4, and m is 0 or 1 Indicates The substrate for forming a printed wiring according to claim 11, wherein the polymer further has at least one structural unit selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4). Resin composition.
<Formula 3>

(In formula (3), R <^9> , R <^10> and i are respectively independently synonymous with R <^9> , R <^10> and i in the said General formula (1), and R <^5> and R <^6> are respectively independently C1-C12 1 Represents an organic group, Z represents a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH-, -COO-, or a divalent organic group having 1 to 12 carbon atoms, e and f represents an integer of 0 to 4, respectively, n represents 0 or 1)
<Formula 4>

(In formula (4), R <^7> , R <^8> , Y, m, g, and h are respectively independently synonymous with R <^7> , R <^8> , Y, m, g, and h in said Formula (2), R <^5> , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in formula (3))